Method and apparatus for excitation of resonances in molecules

ABSTRACT

A method is described to excite molecules at their natural resonance frequencies with sufficient energy to break or form chemical bonds using electromagnetic radiation in the radio frequency (RF) and microwave frequency range. Liquid, solid, or gaseous materials are prepared and injected into a resonant structure where they are bombarded with electromagnetic energy in the RF or microwave range at resonant frequencies of the molecules of the materials. Alternatively, electromagnetic energy tuned to dielectric particles prepared from the materials may also be supplied to further enhance the reaction.

This invention relates generally to processing or reaction of materials.The invention has particular utility in the use of electromagneticenergy at resonance frequencies of the material being reacted upon orprocessed to promote a chemical process or reaction, such as thebreaking of chemical bonds in large molecules and will be described inconnection with such utility, although other utilities are contemplated.An example of this is to break molecular bonds in long hydrocarbonchains so that shorter chain and lower weight hydrocarbons are created.Such a process could for example reduce heavy, viscous oil to a lessviscous consistency so that it can be more easily transported through apipe.

Petroleum-based materials are integral to the world's economy and demandfor petroleum based fuels and petroleum based products is increasing. Asthe demand rises, there is a need to efficiently and economicallyprocess petroleum-based materials to fulfill that demand. As such, itwould be advantageous to not only be able to process raw petroleum-basedmaterials from the earth, but to recycle consumer products to recapturethose petroleum-based materials.

Worldwide oil consumption is estimated at in excess of seventy millionbarrels per day and growing. Thus, there is a need for sufficient oilsupplies. Tar sands, oil sands and oil shales, contain large quantitiesof oil; however, extraction of oil from these materials is costly andtime-consuming.

Pumping heavy oil from oil sands is difficult. Typically, up to 30% byvolume of a solvent or diluent must be added to such oil to make it thinenough to pump through pipelines. This adds a cost of as much as 15% toa barrel of oil at current prices. Thus, the ability to economicallybreak some of the molecular bonds to make the oil less viscous couldhave a significant impact on the recovery of useful products from oilsands. Another problem that is becoming increasingly important is thedisposal of toxic wastes. Generally to render wastes harmless requiresbreaking chemical bonds in the waste and possibly then adding othersubstances to form new bonds.

In prior art, it is known that a process or reaction volume can beexcited in a resonant electromagnetic structure with an electromagneticgenerator coupled to it. The structure is generally multimode (i.e.,multi-spatial mode). A microwave oven is an example of such anapparatus.

The resonant structure also may be a single mode structure, wherein asingle frequency is resonant in a single spatial mode. A single moderesonant structure is smaller than a multimode resonant structure andcannot handle as much power input. In many applications, it is desirableto create a plasma in a process or reaction volume, and it is generallyeasier in a single mode resonant structure to establish a stable plasmaand to maintain matching to the generator and its delivery system.

It also is known that a reaction or process volume can be excited in amultimode resonant structure coupled to a plurality of electromagneticgenerators. For example, U.S. Pat. No. 7,227,097 describes a systemusing multiple generators coupled to a common multimode resonantstructure, with a plasma created in the common resonant cavity. Thisconfiguration has the advantage of permitting more input power, but themultimode cavity is far more sensitive to plasma fluctuations. Matchingand maintaining the electromagnetic generators and their respectivedelivery systems also is difficult in this configuration. There also ismore cross-coupling of the various generators through plasmainstabilities. Prior art references also provide multiple generatorinputs for a single mode resonant structure, but in the single modeconfiguration each generator would be required to have the samefrequency and phase, and the resonant structure would limit how muchpower could be applied.

In many cases, it is necessary to use very high frequencies, for examplemicrowaves. Generation of microwave energy (roughly 300 MHz to 300 GHz)from input electrical energy is typically only about 50 to 70%efficient. By comparison, generation of lower radio frequency (roughly455 KHz to 300 MHz) energy conversion is up to 95% efficient.

In some processes or reactions, it becomes necessary to use microwaveenergy. For example, in many applications it is necessary to form aplasma using microwave frequencies, but it would be very advantageous tofurther heat the plasma using lower frequencies that can be generatedmore efficiently. Further, in a microwave resonant structure, generallythe plasma is not uniformly heated along the length of a process orreaction chamber.

Accordingly, there is a need for an improved method and apparatus fortreating a process volume with increased efficiency. Specifically, it isdesirable to excite the plasma uniformly along the length of thereaction chamber and to utilize lower radio frequency energy conversion.

The present disclosure addresses the needs discussed above by utilizingexcitation of molecules at various of their resonant frequencies tocause bonds to break or form. By exciting the molecules at a naturalresonant frequency, it is possible to provide sufficient excitation tobreak a chemical bond.

Generally the resonant rotational frequencies of molecular bonds are inthe radio frequency (RF) range (455 kHz to 300 MHz) or microwavefrequency range that is from about 300 MHz to 300 GHz, spanning awavelength range from about 150 meters to 1 millimeter. Generally theseare vibrational modes of the molecule.

In the gaseous phase, these resonances are sharp and well defined. Thereare many tabulations of the microwave or RF resonant frequencies ofrotational modes of molecules. If the molecules are in close proximity,as in a liquid or solid, these levels become much broader, butnevertheless there are still regions where absorption of electromagneticradiation is increased.

In our co-pending U.S. application Ser. No. 12/420,770 filed Apr. 8,2009, assigned to a common assignee and incorporated by referenceherein, we provide a system, i.e. a method and apparatus for treating aprocess or reaction volume with multiple electromagnetic generators byapplying the output of several electromagnetic generators to respectiveresonant structures, with the several resonant structures then coupledto a common process or reaction volume. The application furtherdiscloses methods for matching and tuning the electromagnetic generatorsto their respective resonant structures, for controlling the power inputto each resonant structure, and for controlling the phase of any inputsthat have the same resonant frequency. The various resonant structuresare arranged such that the reaction or process volume is a part of eachresonant structure. In this configuration, the generators can havedifferent frequencies and phases, and still be matched to a commonprocess or reaction volume.

Only the process or reaction volume limits the amount of power that canbe inputted. Thus, the system combines the advantages of multiple inputsand increased stability by having each generator coupled to its ownresonant structure, wherein each resonant structure is in turn coupledto the common process or reaction volume.

Our previous disclosure also provide a method and apparatus to couplelower, radio frequency (RF) electromagnetic sources to the reaction andprocess volume in addition to the microwave sources. The disclosurefurther provide for a static magnetic field. In order to accomplishthis, the process or reaction chamber is arranged such that severalmicrowave modes are simultaneously resonant in the structure. Thispermits more even and greater excitation of the material being processedor reacted upon. The structure allows several microwave inputs of thesame or different frequencies. The structure further provides electronicand mechanical tuning for matching of the microwave generators to theprocess or reaction chamber and allows rapid adjustment for maintainingmatching to the load.

The present disclosure further provides a method and apparatus wherebymolecules are excited with an intense microwave or RF electromagneticfield, such that enough energy is added to the molecules to overcome thebonding energy that holds them together. This disclosure also can beused to promote bond forming in chemical reactions.

The present disclosure uses particles (or drops) of the material to beprocessed or reacted upon to serve as dielectric resonators. Largeelectromagnetic fields building up in these small dielectric resonatorswill cause heating and eventual breakdown, breaking some bonds andscattering the material into the resonant chamber, whose resonantfrequency coincides with the natural resonant frequency of theconstituent molecules. There may be many species of material in theoriginal dielectric resonators. The material may he passed throughsuccessive resonant structures to excite other resonant frequencies, orin some cases it may be possible to have several input frequencies tothe resonant structure.

One aspect of the present disclosure provides a method for causing areaction by exciting molecules with radio frequency or microwaveelectromagnetic energy at one or more frequencies tuned to the naturalresonant frequencies of the molecules. The materials are prepared forprocessing by either atomizing or pulverizing to adequately dilute thematerial in order to absorb maximum amounts of energy. The material isthen injected into a resonant structure, wherein the resonant structuresupports electromagnetic fields at the natural resonant frequencies ofthe molecules of the material to be processed. Electromagnetic energyinputs are provided to the resonant structure at frequenciescorresponding to natural resonances of the material to be processed.Finally, the products of the method are collected from the resonantstructure to either be used or subjected to further processing.

Another aspect of the present disclosure provides a method as describedabove wherein a plurality of particles of the material to be processedeach form dielectric resonators. The electromagnetic energy inputs areprovided to the resonant structure at frequencies corresponding tonatural resonances of the dielectric resonators.

Yet another aspect of the present disclosure provides a method asdescribed above, wherein electromagnetic energy inputs are provided tothe resonant structure at frequencies corresponding to naturalresonances of the dielectric resonators and at frequencies correspondingto natural resonances of the molecules of the material to be processed.

Another aspect of the present disclosure is provided in the form of anapparatus for accomplishing the above-described methods, comprising: areaction structure containing a process or reaction volume; and aplurality of electromagnetic generators coupled to the reactionstructure.

Other features of the present disclosure provide for various frequenciesof electromagnetic radiation chosen to selectively favor the productionof a desired product. Further, additional static electromagnetic fieldsmay be applied to orient polar molecules of the material to be processedin such a way as to optimize their interaction with the various appliedelectromagnetic fields.

Other systems, methods, features, and advantages of the presentdisclosure will be or become apparent upon examination of the followingdrawings and detailed description. The features, functions andadvantages that have been discussed can be achieved independently invarious embodiments of the present disclosure or may be combined in yetother embodiments further details of which can be seen with reference tothe following description and drawings.

Many aspects of the disclosure can be better understood with referenceto the following drawings. The components in the drawings are notnecessarily to scale, emphasis instead being placed upon clearlyillustrating the principles of the present disclosure. Moreover, in thedrawings, like reference numerals designate corresponding partsthroughout the several views.

FIG. 1 is a schematic of an apparatus in accordance with the presentdisclosure; and

FIG. 2 is a flowchart of a method for exciting resonances in moleculesin accordance with the present disclosure.

In the following description, reference is made to the accompanyingdrawings, which form a part hereof, and in which is shown, by way ofillustration, various embodiments of the present invention. it isunderstood that other embodiments may be utilized and changes may bemade without departing from the scope of the present invention.

Molecules have many vibrational and rotational modes, with rotationalresonant frequencies generally in the radio or microwave frequencyrange. For very large molecules, such as hydrocarbons that can havehundreds of atoms, there are generally many resonant frequenciesavailable that are closely spaced. At high levels of excitation, andalso in complex molecules with many atoms, the rotational andvibrational levels are coupled, resulting in many levels available toabsorb radio or microwave frequency radiation. If sufficient energy isapplied to a molecule at one or more of the resonant frequencies, moreand more photons will be absorbed, increasing the level of excitation ofthe various resonances until ultimately a chemical bond will be broken,or in some cases a chemical bond may be formed.

The binding energies of molecules are generally of the order of one toseveral electron volts (ev). In order to break a chemical bond in amolecule, an equal amount of energy must be supplied to one of theresonant modes of the molecule. For example, if a reaction is to becaused by the absorption of a single photon, then the photon must havean energy of several electron volts. This amount of energy correspondsto light within the ultraviolet or visible spectrum. A laser, or similarelectromagnetic energy source with an output in the desired wavelengthregion, would probably be required to bring about dissociation.

Since the efficiency of radio and microwave sources is much greater thanlasers, it is desirable to be able to dissociate molecules or form bondswith these sources. Photons in this frequency range have far too littleenergy to cause dissociation or bond formation with a single photon.However, if one of the vibrational or rotational modes (or both) of themolecule can be excited by the absorption of multiple RF or microwavephotons, a reaction may still take place. Where the RF or microwavesource is tuned to resonance of one of the modes, then many quanta ofthe electromagnetic radiation can be absorbed because the probability ofcausing a transition from one energy level to a higher one increases atnatural resonances of the molecule. Further, the probability of atransition also increases with the number of available photons (oralternatively, with the strength of the microwave field).

As discussed above, bond energies in a molecule are generally on theorder of several electron volts. Microwave or RF photons containapproximately 1/100 of the energy required, so a large number photonswould need to be absorbed to break (or form) a chemical bond. There aretwo basic ways this can be accomplished with low energy photons such asthese: multi-photon absorption between two energy levels by means ofso-called virtual intermediate energy levels or repeated absorption ofphotons by real energy levels in the molecule. A combination of both ofthese processes is another viable option. Multi-photon absorption ofinfrared radiation by means of a laser has been demonstrated, and thedissociation of water by a microwave electromagnetic field has also beendemonstrated. However, the microwave radiation was not at a naturalresonant frequency of the water molecules.

It is a purpose of this disclosure to cause excitation and dissociationor bond forming by using intense microwave or RF fields in a mechanicalresonant structure, wherein the structure is resonant at multiplefrequencies, and wherein these resonant frequencies also coincide withresonant frequencies within the molecules to cause bond breaking orforming.

As stated above, enough energy must be added to a molecule to causebreaking of various chemical bonds (or also formation of various bonds).In order to achieve this, it is desirable in some cases to use othermethods to also increase the energy of the molecule. This has been donefor example by forming a plasma where collisions of electrons and otherparticles can add energy.

A further part of this disclosure is to add energy by forming themolecules to be acted upon into small particles or drops of appropriateshapes of uniform size, and then use these particles or drops asdielectric resonators. A particle or drop in fact forms a dielectricresonator with a well defined resonant frequency. If the particles ordrops are injected into a mechanical resonant structure with very largeelectromagnetic fields at the natural resonant frequencies of theparticles or drops, very large electromagnetic fields will be built upinside these small dielectric resonators. These resonant frequenciesgenerally will be in the microwave frequency range. These intense fieldswill cause rupture of the dielectric resonators, scattering fragments ofthe rupture into the mechanical resonant structure. These fragments willinclude excited molecules, fragments of the original molecules due tobond breaking, smaller bits of the original material, and in the eventof other substances deliberately added inside the mechanical resonantstructure, new molecules, where fragments of the original molecules havecombined with the other substances introduced into the chamber. We haveobserved such a process in a reaction cell constructed in accordancewith the apparatus disclosed in our co-pending U.S. application Ser. No.12/234,503 filed Sep. 19, 2008, assigned to a common assignee andincorporated by reference herein. In that case, hydrogenation ofhydrocarbon molecules was observed due to the presence of water in thereaction cell.

Once the dielectric resonators have ruptured, the products can be actedupon by intense resonant electromagnetic fields of the properfrequencies to cause selective excitation of the various products fromthe rupture of the dielectric resonators, in order to add still moreexcitation to the molecules ultimately to achieve bond breaking or bondformation.

It is a purpose of this disclosure to provide intense microwave or RFelectromagnetic radiation at frequencies exactly coinciding with naturalmolecular resonances of molecules of a substance to cause eitherdissociation or bond forming. This will involve injecting the substanceto be reacted upon or processed into a structure that is resonant at theRF and/or microwave frequencies. Generally the substance will be in adilute form so that the resonances of the molecules which comprise thesubstance are heightened, although as explained previously, even incondensed form molecules retain resonant features, although not as sharpas in dilute form.

In sum, molecules are excited by three resonant processes. First, theelectromagnetic fields are enhanced by being in a mechanical structurethat is resonant at the RF or microwave frequency. Secondly, thisresonant frequency is chosen to coincide with one or more of the naturalresonant frequencies of the constituent molecules. Additionally, asexplained previously, the molecules of the substance can be formed intodielectric resonators to further add energy.

More than one species of molecules can be acted on at once byappropriately choosing multiple resonant frequencies, and othermaterials can be added to promote bond breaking or bond formation.Catalysts or particles of other substances also can be added to promotebond breaking, bond forming, and/or energy transfer to the molecules(for example small metal particles to act as “seeds” for drop formation

FIG. 1 shows one embodiment of this disclosure. In this case, we havechosen a liquid as an input to the process. The liquid is atomized intoa fine mist and injected into a resonant structure whose resonantfrequency coincides with one of the natural resonant frequencies of themolecules that comprise the liquid. In this case, it is desirable tobreak some of the chemical bonds of the molecules. This would be done,for example, to break complex heavy hydrocarbon molecules, such as occurin heavy petroleum, into other shorter molecules. This would be done tomake other products or synthesize new ones. One other application ofthis is to make the oil less viscous so that it can be pumped through apipe.

FIG. 1 displays a liquid 1 which is shown for illustrative purposes, buta solid or a gas alternatively could be used, with appropriatemodifications to the apparatus. The liquid is pumped by a pump 2 throughan atomizer 3 to create liquid droplets 4. Element 5 is a resonantstructure with high microwave and possibly also RF electromagneticfields. Generators 6, 7, 8, and 9 in this illustration arc shown asmicrowave sources, coupled to the resonant structure by a couplingdevice, such as a waveguide or a coaxial cable 10,11,12,13, andappropriate impedance matching devices 14,15,16,17. The generators6,7,8,9 may be the same or different frequencies. There also may be moreor less than four generators. Lower frequency RF sources 18, 19 are foradding more power into the resonant structure. The resonant structure 5can be constructed so that parts of it form an inductor that can beresonant with an appropriate capacitance, shown schematically by 20 and21 in the figure. The capacitance can also be a part of the resonantstructure, so that separate-capacitors are not needed. A technique formaking the structure resonant at these lower frequencies is disclosed inthe afore-mentioned, commonly owned applications. A static magnetic orelectric field also can be added to the resonant structure to confine aplasma if one is generated or to align polar molecules for moreefficient absorption of electromagnetic radiation. This is shownschematically as a DC source 22.

It is to be understood that the disclosure is not limited to thegenerators shown. Additional generators can be used for more power whereappropriate. Systems for matching multiple generators of differentfrequencies to the same load are disclosed in the afore-mentioned,commonly owned applications.

The input liquid is atomized into spheres by an atomizer 3. Thespherical drops 4 are in fact dielectric resonators, and if one of theinput frequencies is chosen properly, very high electromagnetic fieldscan be built up inside the droplets, leading to very high levels ofexcitation of the molecules in the droplet. When the energy reaches acertain point, this can cause a “spark” to occur, breaking the molecularbonds and scattering molecules into the resonant chamber, where anotherelectromagnetic field whose frequency has been chosen to be at one ofthe molecule's natural frequencies will further excite that resonance.This can be used either to break a bond or to facilitate a chemicalreaction (such as form new bonds). In the latter case, another substancewould also be injected into the resonant structure to combine with theexcited molecules or atoms.

Products 24 from the reaction or process are collected at the output ofthe apparatus. The entire resonant structure is contained in anelectromagnetic shield to prevent radiation into the environment.

FIG. 2 illustrates the method of the present disclosure. A material isprepared and injected into a resonant structure. Electromagnetic energyis provided at resonant frequencies of the prepared material, causing areaction of the material in the form of breaking molecular bonds and/orforming new chemical bonds with other materials present in the resonantstructure. The products of the reaction are then collected, wherein someproducts may be useful for other processes and other products mayrequire further processing.

The radio frequencies are typically in the RF range (455 kHz to 300 MHz)and/or microwave range (300 MHz to 300 GHz). The material may beprepared, for example, by atomizing a liquid prior to injecting into theresonant structure. Alternatively, the material may be a solid that hasbeen pulverized into a plurality of small particles, wherein some of theparticles may be spherical. The input material also could be a gas, or acombination of any of the materials discussed herein. A catalyst alsomay be injected into the resonant structure to facilitate a reaction orto react with the prepared materials to form new materials.

It should be emphasized that the above-described embodiments of thepresent disclosure, particularly, any “preferred” embodiments, aremerely possible examples of implementations, merely set forth for aclear understanding of the principles of the present disclosure. Manyvariations and modifications may be made to the above-describedembodiments without departing substantially from the spirit andprinciples of the disclosure. All such modifications and variations areintended to be included herein within the scope of this disclosure andprotected by the following claims.

1-33. (canceled)
 34. An apparatus for exciting a process medium withelectromagnetic radiation comprising: a reaction structure containing aprocess or reaction volume; and a plurality of electromagneticgenerators coupled to the reaction structure.
 35. The apparatus of claim34, further comprising at least one static electromagnetic generatorcoupled to the reaction structure.
 36. The apparatus of claim 34,wherein the electromagnetic generators are tuned to frequencies in therange of radio frequencies and microwave frequencies.
 37. The apparatusof claim 34, wherein the electromagnetic generators are coupled to thestructure by either a waveguide or a coaxial cable.
 38. The apparatus ofclaim 34, wherein the material to be processed is selected from thegroup consisting of: a liquid; a solid; a gas; and a combination of aliquid, a solid and a gas.
 39. The apparatus of claim 38, wherein thematerial to be processed is a liquid, wherein the apparatus furthercomprises an atomizer for atomizing the liquid for injection into theresonant structure.
 40. The apparatus of claim 38, wherein the materialto be processed is a solid, and wherein the apparatus further comprisesa pulverizer for pulverizing the solid into small particles forinjection into the resonant structure.